CN104449960A - Composite calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof - Google Patents

Composite calcium sulfonate-calcium naphthenate-based polyurea grease and preparation method thereof Download PDF

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CN104449960A
CN104449960A CN201310419090.3A CN201310419090A CN104449960A CN 104449960 A CN104449960 A CN 104449960A CN 201310419090 A CN201310419090 A CN 201310419090A CN 104449960 A CN104449960 A CN 104449960A
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calcium
acid
weight
add
naphthenate
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CN104449960B (en
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何懿峰
孙洪伟
刘中其
段庆华
张建荣
姜靓
陈政
郑会
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses composite calcium sulfonate-calcium naphthenate-based polyurea grease. The composite calcium sulfonate-calcium naphthenate-based polyurea grease comprises, by weight, 10-70% of non-Newtonian calcium sulfonate-calcium naphthenate, 1-20% of higher fatty acid calcium salt, 1-15% of aromatic acid calcium salt, 0.5-30% of a polyurea compound and 10-80% of base oil, and optionally comprises, by weight, 1-15% of micromolecular inorganic acid and/or lower fatty acid calcium salt. The invention also discloses a preparation method of the composite calcium sulfonate-calcium naphthenate-based polyurea grease and the composite calcium sulfonate-calcium naphthenate-based polyurea grease obtained by the preparation method. Compared with the composite calcium sulfonate-based polyurea grease, the composite calcium sulfonate-calcium naphthenate-based polyurea grease has better mechanical stability, water resistance, adhesion resistance, salt mist resistance and extreme pressure antiwear property and a longer service life.

Description

A kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease and preparation method thereof
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease and preparation method thereof.
Background technology
Calcium sulphonate is used as the history that the purification agent of lubricating oil and rust-preventive agent have decades, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active alkyl benzene calcium sulfonate or alkyl carboxylic acid calcium.Calcium sulfonate with high base number can be divided into calcium mahogany sulfonate and calcium alkylbenzenesulfonate according to mode of production difference.Calcium mahogany sulfonate is with oleum or SO 3sulfonation mineral lubricating oils produces by product mahogany acid during white oil, warp and Ca (OH) 2reaction, the contour alkalization technology of carbonating and obtaining; Calcium alkylbenzenesulfonate is with oleum or SO 3the alkylbenzene of sulfonation synthesis, alkyl benzene sulphonate (ABS) warp and Ca (OH) of generation 2reaction, the contour alkalization technology of carbonating and obtaining.
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH) 2reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has CN1465560 etc.
Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, but, although high base number composite calcium sulfonate base grease has very excellent over-all properties, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, simultaneously, along with the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and high base number composite calcium sulfonate base grease is similar but the lubricating grease that can alleviate the problems referred to above becomes the large problem that people face at present.
Summary of the invention
The object of this invention is to provide a kind of performance and high base number composite calcium sulfonate base grease is similar, cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The calcium salt of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid.Performance and the high base number composite calcium sulfonate base grease of this lubricating grease are similar, and cost is low, and preparation technology is simple, environmental protection.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The calcium salt of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The calcium salt of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid.
Second aspect, the invention provides the preparation method of complex calcium sulfonate as above-Calcium naphthenate base polyurea grease, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, polyurea compound, oily and optionally small molecules mineral acid and/or lower fatty acid the calcium salt of part basis are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides the preparation method of a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides the complex calcium sulfonate-Calcium naphthenate base polyurea grease obtained by method as above.
Complex calcium sulfonate of the present invention-Calcium naphthenate base polyurea grease, not only the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of lubricating grease prepared by embodiment 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, this lubricating grease have employed calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and petroleum naphthenic acid calcium and/or synthesis calcium naphthenate be raw material, simultaneously containing composite calcium viscosifying agent, isocyanic ester and amine reaction produce polyurea compound.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The calcium salt of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The calcium salt of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid.
In the present invention, " optionally also comprise " and refer to comprise and also can not comprise, that is, the calcium salt of small molecules mineral acid and/or lower fatty acid is selectable components, this component can be comprised in complex calcium sulfonate of the present invention-calcium naphthenate base grease, also can not comprise this component.
Described non-newtonian fluid calcium sulphonate-calcium naphthenate is at infrared spectrum 873cm -1-886cm -1there is crystal form calcium carbonate charateristic avsorption band in place, total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium sulphonate-calcium naphthenate is obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium sulphonate, newton's body calcium naphthenate, at infrared spectrum 860cm -1-865cm -1there is unformed calcium carbonate charateristic avsorption band in place.Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.The base number of non-newtonian fluid calcium sulphonate-calcium naphthenate is the weight mean value of the base number of newton's body calcium sulphonate and the base number of newton's body calcium naphthenate.
In the present invention, higher fatty acid is carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, at least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, is preferably 12-oxystearic acid.
In the present invention, aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, aromatic acid can be replace or unsubstituted aromatic acid, its substituting group can be at least one in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, such as, can be selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Be preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and at least one in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.
In the present invention, described polyurea compound is without particular requirement, and the polyurea compound can commonly used for this area can be such as at least one in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.Wherein the weight ratio of two polyurea compounds, four polyurea compounds, six polyurea compounds, eight polyurea compounds can be arbitrary proportion.More preferably described polyurea compound is two polyurea compounds.
In the present invention, described two polyurea compounds preferably have following structure:
Wherein, R 1, R 1 'can be the same or different, can be alkyl, cycloalkyl or aryl, and the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R 3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R 3be more preferably in at least one.
In the present invention, described four polyurea compounds preferably have following structure:
Wherein, R 1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of phenyl or replacement, is preferably the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R 2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R 3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R 3be more preferably in at least one.
In the present invention, described six polyurea compounds preferably have following structure:
Wherein, R 1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R 2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R 3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R 3be more preferably in at least one.
In the present invention, described eight polyurea compounds preferably have following structure:
Wherein, R 1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, and be preferably 10-18, aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R 2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, and be preferably 2-8, arylidene can be phenylene or biphenylene.
Wherein, R 3can be arylidene, alkylidene group or cycloalkylidene, the carbon number of arylidene, alkylidene group or cycloalkylidene can be 6-30, is preferably 6-20, R 3be more preferably in at least one.
Above-mentioned polyurea compound can adopt the thinkable various method of those skilled in the art institute to obtain, and the method such as can recorded according to CN103060069A, CN103060070A, CN103060068A, CN103060067A prepares.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-150mm 2/ s, is preferably 10-60mm 2/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
In the present invention, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from least one in boric acid, phosphoric acid, sulfuric acid etc., is preferably boric acid and/or phosphoric acid; Lower fatty acid can be selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., is preferably acetic acid.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides the preparation method of complex calcium sulfonate as above-Calcium naphthenate base polyurea grease, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, polyurea compound, oily and optionally small molecules mineral acid and/or lower fatty acid the calcium salt of part basis are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, " optionally the calcium salt of small molecules mineral acid and/or lower fatty acid " refers to that the raw material preparing complex calcium sulfonate-calcium naphthenate base grease can comprise the calcium salt of small molecules mineral acid and/or lower fatty acid, also the calcium salt of small molecules mineral acid and/or lower fatty acid can not be comprised, that is, the calcium salt of small molecules mineral acid and/or lower fatty acid is optional raw material or a component.
In the present invention, described above for the calcium salt of the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, small molecules mineral acid and/or lower fatty acid, polyurea compound, base oil and additive, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.1-5 with the weight ratio of surplus base oil.
For non-newtonian fluid calcium sulphonate-calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium sulphonate and newton's body calcium naphthenate, such as, by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute, be then warming up to 100-120 DEG C of dehydration.
The third aspect, the invention provides the preparation method of a kind of complex calcium sulfonate-Calcium naphthenate base polyurea grease, comprising:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
In step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute.
In the present invention, for the weight ratio of newton's body calcium sulphonate and newton's body calcium naphthenate without particular requirement, be preferably 1:0.25-4.The gross weight of newton's body calcium sulphonate and newton's body calcium naphthenate and the weight ratio of part basis oil are preferably 1:0.1-3.
Described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g, is preferably 300mgKOH/g-400mgKOH/g.
Described transforming agent is preferably selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water; More preferably at least one in the fatty alcohol of C1-C5, the lipid acid of C1-C5, the aliphatic ketone of C1-C5, the alkanoic of C1-C5, the aliphatic amide of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, the arylphosphonic acid of C6-C20, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate (ABS) and water is selected from; Further be preferably selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water.The add-on of transforming agent is preferably the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight, is more preferably the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
In the present invention, fatty alcohol comprises the fatty alcohol of straight chain, side chain and ring-type, and lipid acid, aliphatic ketone, alkanoic, aliphatic amide are in like manner.
In step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add aromatic acid and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C, preferably keep 30-60 minute to realize dehydration.Wherein, the addition sequence of higher fatty acid and aromatic acid, small molecules mineral acid and/or lower fatty acid can exchange.
In the present invention, " optionally small molecules mineral acid and/or lower fatty acid " refers in step (2) can comprise small molecules mineral acid and/or lower fatty acid, also small molecules mineral acid and/or lower fatty acid can not be comprised, that is, small molecules mineral acid and/or lower fatty acid are optional raw materials.
In the present invention, higher fatty acid, aromatic acid, small molecules mineral acid, lower fatty acid as previously mentioned, do not repeat them here.
In the present invention, the H of higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid +oH contained by the suspension liquid of total amount of substance and lime or calcium hydroxide -total amount of substance is equal, OH -amount also can excessive 1-10%.
In the present invention, in calcium hydroxide, the add-on of the suspension liquid of lime or calcium hydroxide is preferably the 1-15% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight; With H +amount of substance meter, the mol ratio of higher fatty acid and aromatic acid and optionally small molecules mineral acid and/or lower fatty acid is preferably 1:1-10.
In the present invention, namely the suspension liquid of lime or calcium hydroxide refers to the suspension liquid that lime or calcium hydroxide are formed in water, and the solid content of suspension liquid is preferably 10-60 % by weight.
In step (3), base oil and monoamine is added in step (2) gained mixture, or also add diamines, add vulcabond to react, namely be prepare polyurea compound in step (2) gained mixture, mixing polyureas can be prepared, also can prepare two independent polyurea compounds, four polyurea compounds, six polyurea compounds or eight polyurea compounds.
The method preparing mixing polyureas, without particular requirement, can adopt the thinkable various method of those skilled in the art, such as, can adopt the method for US Patent No. 3243372.
Prepare the method for two polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and monoamine in step (2) gained mixture, stir 2-8 minute, then add the vulcabond be dissolved in base oil, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.
Prepare the method for four polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, can add base oil and vulcabond, stir, add diamines in step (2) gained mixture, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of vulcabond, diamines and monoamine is 2:1:2.
Prepare the method for six polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, stir, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of added successively vulcabond, monoamine, diamines and vulcabond is 2:2:2:1.
Prepare the method for eight polyurea compounds without particular requirement, the various methods that this area is conventional can be adopted.Such as, in the present invention, base oil and vulcabond can be added in step (2) gained mixture, stir, add diamines, stir 2-8 minute, again add diamines, stir 2-8 minute, add monoamine, stir 2-8 minute, the mol ratio of added successively vulcabond, diamines, diamines and monoamine is 4:2:1:2.
Described vulcabond structure is OCN-R 3-NCO, R 3can be carbon number be 6-30, the arylidene of preferred 6-20, alkylidene group or cycloalkylidene, be preferably deng.Such as, described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl vulcabond (HMDI) and an xylylene diisocyanate (XDI) etc.
Described monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R 1-NH 2, R 1 '-NH 2, R wherein 1, R 1 'can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferred 10-18, and aryl can be the phenyl of the phenyl of phenyl or replacement, preferred phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Described diamines can be aliphatic amide or arylamine, and structural formula is NH 2-R 2-NH 2, R wherein 2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2-12, preferred 2-8, and arylidene can be phenylene or biphenylene.Preferred diamines can be selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
In step (4), first at 100-120 DEG C of constant temperature 10-20 minute, be finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
In the present invention, in step (1), in the total amount of base oil used and step (3), in the total amount of base oil used and step (4), the weight ratio of the total amount of base oil used is preferably 1:0.1-5:0.1-5.
Fourth aspect, the complex calcium sulfonate that the preparation method that present invention also offers is provided by third aspect present invention obtains-Calcium naphthenate base polyurea grease.
Compared with the complex calcium sulfonate obtained with the preparation method provided by second aspect-Calcium naphthenate base polyurea grease, the complex calcium sulfonate that the preparation method that the third aspect provides obtains-Calcium naphthenate base polyurea grease has and better has better mechanical stability, water resisting property and adhesivity, colloid stability, extreme pressure anti-wear, and has longer lubricating life.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Overbased or calcium sulfonate with high base number raw material weight+the overbased or overbased calcium alkyl-salicylate raw material weight+transforming agent gross weight of non-newtonian fluid calcium sulphonate-calcium naphthenate %=()/lubricating grease gross weight × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium sulphonate-calcium naphthenate.
Overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Overbased and calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Naphthenic acid is purchased from Jinzhou Tie Chen petrochemical complex limited liability company.
Embodiment 1
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 17kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, stir 4 minutes, add the 0.7kg MDI be dissolved in the HVI500SN lubricating base oil of 2kg again, stir 4 minutes, added MDI is 1:2 with the ratio of the amount of substance of stearylamine, 120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Embodiment 2
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 17kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the naphthenate with superhigh base number calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation; Be warmed up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, under stirring, be warmed up to 120 DEG C, keep 30 minutes, dehydration;
Another volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, be warming up to 120 DEG C, stir 4 minutes, add the 0.7kg MDI dissolved with 2kg HVI500SN lubricating base oil, stir 4 minutes, added MDI and the mol ratio of stearylamine are 1:2, and 120 DEG C of constant temperature 20 minutes, obtains two polyureas.
Gained two polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Embodiment 3
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 20kg); Propyl carbinol (3.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); Stearic acid (1.9kg); Phthalic acid (3.5kg); Lauryl amine (1.31kg); MDI(0.89kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 27kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, 6kg total basicnumber is the overbased calcium alkyl-salicylate of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir, heat to 80 DEG C, constant temperature 10 minutes; Add 3.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 90 DEG C, constant temperature 60 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 1.9kg stearic acid, stir 10 minutes; Add 3.5kg phthalic acid, stir 10 minutes, under stirring, be warmed up to 100 DEG C, keep 60 minutes, dehydration; Add HVI500SN lubricating base oil and the 1.31kg lauryl amine of 2kg, stir 8 minutes, add the 0.89kg MDI be dissolved in the HVI500SN lubricating base oil of 4kg again, stir 8 minutes, added MDI is 1:2 with the ratio of the amount of substance of lauryl amine, 100 DEG C of constant temperature 10 minutes, is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, remaining HVI500SN lubricating base oil is added; Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.9 % by weight; Calcium stearate 2.3 % by weight; Calcium phthalate 4.8 % by weight.
Embodiment 4
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 25kg); Witco 1298 Soft Acid (2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); M-phthalic acid (3.5kg); Stearylamine (1.66kg); TDI(0.54kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 22kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Replace naphthenic acid with Witco 1298 Soft Acid simultaneously; Terephthalic acid is replaced with m-phthalic acid; MDI is replaced with TDI; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; M-phthalic acid calcium 4.8 % by weight.
Embodiment 5
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 24kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 1.8kg); Boric acid (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 7kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Transforming agent is naphthenic acid, boric acid and acetic acid, and its mesoboric acid adds after acetic acid; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 52.1 % by weight; Two polyureas 3.5 % by weight; Lubricating base oil 34.4 % by weight; 12-oxystearic acid calcium 3.3 % by weight; Terephthalic acid calcium 6.7 % by weight.
Embodiment 6
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 25kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); 4,4'-biphenyl dicarboxylic acid (5.1kg); Stearylamine (4.5kg); MDI(2.1kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 18.6kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, use 4,4'-biphenyl dicarboxylic acid to replace terephthalic acid; Transforming agent is only naphthenic acid and acetic acid, saves the step adding methyl alcohol; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.4 % by weight; Two polyureas 7.2 % by weight; Lubricating base oil 47.6 % by weight; 12-oxystearic acid calcium 2.3 % by weight; 4,4'-biphenyl dicarboxylic acid calcium 6.5 % by weight.
Embodiment 7
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); Full synthetic oil poly & Alpha ,-olefin oil PAO40(100 DEG C of kinematic viscosity is 41mm 2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); Full synthetic oil poly & Alpha ,-olefin oil PAO10(100 DEG C of kinematic viscosity is 11mm 2/ s, 9kg); Dithio Acidic phosphates zinc (2kg); Molybdenum dialkyldithiocarbamacompositions (1kg); Tungsten disulfide (2kg); Two tungsten selenide (2kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Transforming agent is only naphthenic acid and acetic acid, saves the step adding methyl alcohol; Full synthetic oil poly & Alpha ,-olefin oil PAO40 and PAO10 is used to replace HVI150BS and HVI500SN respectively; And treat that temperature is cooled to 110 DEG C, add the dithio Acidic phosphates zinc of 2kg, stir 10 minutes, add the molybdenum dialkyldithiocarbamacompositions of 1kg, stir 10 minutes, add the tungsten disulfide of 2kg, stir 10 minutes, add two tungsten selenide of 2kg, stir 10 minutes, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.8 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 44.2 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.9 % by weight; Dithio Acidic phosphates zinc 2.3 % by weight; Molybdenum dialkyldithiocarbamacompositions 1.1 % by weight; Tungsten disulfide 2.3 % by weight; Two tungsten selenide 2.3 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 8
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); 2-methyl isophthalic acid, 4-phthalic acid (3.8kg); Stearylamine (0.94kg); Para-totuidine (0.38kg); MDI(0.88kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 33kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g; Transforming agent is only naphthenic acid and acetic acid, saves the step adding methyl alcohol; Use 2-methyl isophthalic acid, 4-phthalic acid replaces terephthalic acid; Monoamine, except stearylamine, also adds para-totuidine, and the consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.1 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 53.3 % by weight; 12-oxystearic acid calcium 2.4 % by weight; 2-methyl isophthalic acid, 4-phthalic acid calcium 4.8 % by weight.
Embodiment 9
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: calcium sulfonate with high base number (total basicnumber is 320mgKOH/g, 6kg); Overbased calcium alkyl-salicylate (total basicnumber is 320mgKOH/g, 24kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 20kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (5.2kg); 12-oxystearic acid (2kg); Boric acid (2.32kg); Terephthalic acid (7.6kg); Stearylamine (0.84kg); Lauryl amine (0.58kg); MDI(0.78kg); HVI500SN lubricating base oil (100 DEG C of kinematic viscosity are 11mm2/s, 28kg); Right, right '-di-iso-octyldiphenylamine (0.2kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, calcium sulphonate uses the calcium sulfonate with high base number that total basicnumber is 320mgKOH/g, and calcium naphthenate uses the overbased calcium alkyl-salicylate that total basicnumber is 320mgKOH/g; Transforming agent is only naphthenic acid and acetic acid, saves the step adding methyl alcohol; Add after 12-oxystearic acid stirs 10 minutes, add boric acid, stir 10 minutes, then add terephthalic acid, stir 10 minutes; And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right '-di-iso-octyldiphenylamine, stir 10 minutes, then circulating filtration, homogenizing, degassedly obtain finished product; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 34.2 % by weight; Two polyureas 2.2 % by weight; Lubricating base oil 49.2 % by weight; 12-oxystearic acid calcium 2.2 % by weight; Lime borate 2.4 % by weight; Terephthalic acid calcium 9.6 % by weight; Right, right '-di-iso-octyldiphenylamine 0.2 % by weight.
Embodiment 10
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 15kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 15kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 15kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Acetic acid (0.56kg); Calcium hydroxide (3kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Acetic acid (2kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 33kg).
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, transforming agent is only naphthenic acid and acetic acid, saves the step adding methyl alcohol; And add after terephthalic acid stirs 10 minutes, add acetic acid, stir 10 minutes, be then under agitation warmed up to 120 DEG C, keep 30 minutes, dehydration; The consumption of each composition as above.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 36.0 % by weight; Two polyureas 2.4 % by weight; Lubricating base oil 51.8 % by weight; 12-oxystearic acid calcium 2.3 % by weight; Terephthalic acid calcium 4.7 % by weight; Lime acetate 2.8 % by weight.
Embodiment 11
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Feed composition: overbased calcium sulphonate (total basicnumber is 400mgKOH/g, 24kg); Naphthenate with superhigh base number calcium (total basicnumber is 400mgKOH/g, 6kg); (100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil 2/ s, 30kg); Naphthenic acid (total acid value is 180mgKOH/g, 2.8kg); Methyl alcohol (1kg); Acetic acid (0.56kg); Calcium hydroxide (1.8kg); 12-oxystearic acid (2kg); Terephthalic acid (3.5kg); Stearylamine (1.5kg); MDI(0.7kg); (100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil 2/ s, 17kg).
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium sulphonate that 24kg total basicnumber is 400mgKOH/g, naphthenate with superhigh base number calcium that 6kg total basicnumber is 400mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm 2the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 2.8kg naphthenic acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2.8kg concentration is 20 % by weight, stir 10 minutes; Be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add the HVI500SN lubricating base oil of 5kg, be warming up to 100 DEG C, add the calcium hydroxide suspension liquid 9kg that solid content is 20 % by weight, stir 10 minutes; Add 2kg12-oxystearic acid, stir 10 minutes; Add 3.5kg terephthalic acid, stir 10 minutes, obtain 12-oxystearic acid calcium and terephthalic acid calcium.
The 3rd volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add HVI500SN lubricating base oil and the 1.5kg stearylamine of 2kg, stir 6 minutes, add the 0.7kg MDI dissolved with the HVI500SN lubricating base oil of 2kg again, stir 6 minutes, 120 DEG C of constant temperature 20 minutes, obtains two polyureas.
The 12-oxystearic acid calcium of gained and terephthalic acid calcium are all squeezed in first still, stirs, under stirring, be warmed up to 120 DEG C, keep 30 minutes, two polyureas of the 3rd reactor gained are all squeezed in this still by dehydration, stir, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add remaining HVI500SN lubricating base oil; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Embodiment 12
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add calcium sulfonate with high base number that 10kg total basicnumber is 350mgKOH/g, (100 DEG C of kinematic viscosity are 31mm to the HVI150BS lubricating base oil of naphthenate with superhigh base number calcium that 20kg total basicnumber is 400mgKOH/g and 25kg 2/ s, lower same), stir, heat to 60 DEG C, constant temperature 10 minutes; Add 3kg naphthenic acid, temperature controls at about 60 DEG C, stirs 10 minutes; Add the 12.5kg butanols aqueous solution that concentration is 20%, stir 10 minutes; 87 DEG C of constant temperature 70 minutes, material retrogradation.
Volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle B in add the HVI500SN lubricating base oil of 5kg (100 DEG C of kinematic viscosity be 11mm 2/ s, lower same), be warming up to 90 DEG C, add the calcium hydroxide suspension liquid 21kg that solid content is 20 % by weight, stir 10 minutes, add the palmitinic acid of 2.4kg, stir 10 minutes, add the oxalic acid of the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and 2kg, stir 10 minutes, obtain calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and oxalic acid calcium.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add the HVI500SN lubricating base oil of 5kg and 1kg MDI rapidly pre-warming to 90 DEG C, 0.12kg quadrol is added under rapid stirring, stir 4 minutes, add 1.08kg stearylamine and stir 4 minutes, the mol ratio of added MDI, quadrol and stearylamine is 2:1:2,120 DEG C of constant temperature 20 minutes, obtains four polyureas.
Volume be 30L and with heating, stir, circulation, cooling normal-pressure reaction kettle D in add 10kg100 DEG C of kinematic viscosity be 11mm 2hVI500SN lubricating base oil and the 0.78kg MDI of/s are preheating to 90 DEG C, 0.84kg stearylamine is added under rapid stirring, stir 4 minutes, 0.19kg quadrol is added under rapid stirring, stir 4 minutes, add 0.39kg MDI, the mol ratio of added successively MDI, stearylamine, quadrol and MDI is 2:2:2:1,120 DEG C of constant temperature 20 minutes, obtains six polyureas.
Gained calcium palmitate, biphenyl dicarboxylic acid calcium, calcium phosphate and oxalic acid calcium are all squeezed in reactor A, stir, 120 DEG C are warmed up under stirring, keep 30 minutes, dehydration, gained four polyureas and six polyureas are all squeezed in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, be cooled to 150 DEG C, add the HVI500SN lubricating base oil of 8kg; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 34.4 % by weight; Calcium palmitate 2.7 % by weight; Biphenyl dicarboxylic acid calcium 4.2 % by weight; Calcium phosphate 1.6 % by weight; Oxalic acid calcium 2.9 % by weight; Four polyureas 2.3 % by weight; Six polyureas 2.3 % by weight; Lubricating base oil 49.6 % by weight.
Embodiment 13
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle A in add overbased calcium sulphonate that 20kg total basicnumber is 400mgKOH/g, 10kg total basicnumber is the naphthenate with superhigh base number calcium of 420mgKOH/g and the HVI150BS lubricating base oil of 10kg, stir, heat to 50 DEG C, constant temperature 10 minutes; Add 2kg Witco 1298 Soft Acid, temperature controls at about 50 DEG C, stirs 10 minutes; Add 1kg methyl alcohol, stir 10 minutes; Add the aqueous acetic acid that 2kg concentration is 20 % by weight, stir 10 minutes; 83 DEG C of constant temperature 80 minutes, material retrogradation.
Volume be 10L and with heating, stir, circulation, cooling normal-pressure reaction kettle B in add the HVI500SN lubricating base oil of 8kg, the calcium hydroxide suspension liquid 8.0kg that solid content is 50 % by weight is added at 85 DEG C, stir 10 minutes, add the lauric acid of 2.4kg, stir 10 minutes, add the m-phthalic acid of 7.9kg, stir 10 minutes, obtain calcium laurate and m-phthalic acid calcium.
Volume be 20L and with heating, stir, circulation, cooling normal-pressure reaction kettle C in add the HVI500SN lubricating base oil of 10kg and 1.17kg MDI is preheating to 80 DEG C, the mixture of 0.84kg stearylamine, 0.19kg quadrol is added under rapid stirring, the mol ratio of added MDI, monoamine, diamines is 3:2:2,120 DEG C of constant temperature 20 minutes, obtains mixing polyureas.
Gained calcium laurate and m-phthalic acid calcium are all squeezed in reactor A, stir, be warmed up to 110 DEG C under stirring, keep 45 minutes, dehydration, all squeezes into gained mixing polyureas in reactor A, stirs, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, the HVI500SN lubricating base oil of 2kg is added; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 41.7 % by weight; Calcium laurate 3.3 % by weight; M-phthalic acid calcium 12.1 % by weight; Polyurea compound 5.4 % by weight; Lubricating base oil 37.5 % by weight.
Embodiment 14
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with phenol, acetic acid is replaced with butyric acid, methyl alcohol is replaced with acetone.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Embodiment 15
Complex calcium sulfonate-Calcium naphthenate base polyurea grease that the present embodiment is prepared for illustration of the present invention.
Complex calcium sulfonate-Calcium naphthenate base polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenic acid is replaced with ketone, aqueous acetic acid is replaced with ether, methyl alcohol is replaced with ethamine.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate-calcium naphthenate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Comparative example 1
Composite calcium-sulfonate-batetrapolyurea two polyurea grease is prepared according to the method for embodiment 1, unlike, naphthenate with superhigh base number calcium total basicnumber is that the overbased calcium sulphonate of 400mgKOH/g replaces, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 37.5 % by weight; Two polyureas 2.5 % by weight; Lubricating base oil 52.8 % by weight; 12-oxystearic acid calcium 2.4 % by weight; Terephthalic acid calcium 4.8 % by weight.
Embodiment 1 and comparative example 1 are compared and can find out, the prolongation Drawing cone in-degree of complex calcium sulfonate of the present invention-Calcium naphthenate base polyurea grease and the difference of Drawing cone in-degree are less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, water drenches number of dropouts much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, salt-fog test is better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, water resistant spraying value is less than Composite calcium-sulfonate-batetrapolyurea polyurea grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea polyurea grease, tetra-ball machine test is greater than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the bearing lubrication life-span is greater than Composite calcium-sulfonate-batetrapolyurea polyurea grease, the mechanical stability of complex calcium sulfonate of the present invention-Calcium naphthenate base polyurea grease is described, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear, lubricating life is all better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, and complex calcium sulfonate of the present invention-Calcium naphthenate base polyurea grease is the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease has the performances such as excellent non-corrosibility and high thermal resistance.
Embodiment 1 is compared can find out with embodiment 2 and embodiment 11 respectively, complex calcium sulfonate-Calcium naphthenate base polyurea grease prepared by original position, there is better mechanical stability, water resisting property and adhesivity, colloid stability, extreme pressure anti-wear, and there is longer lubricating life; Embodiment 1 is compared can find out with embodiment 14 and embodiment 15 respectively, transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, butanols, Virahol, boric acid, acetic acid and water, complex calcium sulfonate-Calcium naphthenate base the polyurea grease of preparation, there is better mechanical stability, water resisting property and adhesivity, colloid stability, extreme pressure anti-wear, and there is longer lubricating life.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326;
Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Steel
Net point oil: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
Table 1(continues) each lubricating grease properties of sample data
each indication test method: dropping point: GB/T3498; Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T269; Corrosion: GB/T7326;
Non-corrosibility: GB/T5018; Water drenches number of dropouts: SH/T0109; Salt-fog test: SH/T0081; Water resistant is sprayed: SH/T0643; Steel
Net point oil: SH/T0324; Tetra-ball machine test: SH/T0202; The bearing lubrication life-span: ASTM D3336.
As can be seen from Figure 1, the lubricating grease of embodiment 2 preparation is at 873cm -1-886cm -1there is crystal form calcium carbonate charateristic avsorption band in place.Meanwhile, at 3300cm -1-3323cm -1the peak at place is the stretching vibration absorption peak of-NH-in two polyureas molecules.
Complex calcium sulfonate of the present invention-Calcium naphthenate base polyurea grease, not only the same with Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is excellent non-corrosibility and high thermal resistance, but also there is the performance such as mechanical stability, water resisting property and adhesivity, resistance to salt(spray)fog, colloid stability, extreme pressure anti-wear being better than Composite calcium-sulfonate-batetrapolyurea polyurea grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (29)

1. complex calcium sulfonate-Calcium naphthenate base polyurea grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 10-70 % by weight; The calcium salt of the higher fatty acid of 1-20 % by weight; The calcium salt of the aromatic acid of 1-15 % by weight; The polyurea compound of 0.5-30 % by weight; The base oil of 10-80 % by weight; Optionally also comprise the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium sulphonate-calcium naphthenate of 20-65 % by weight; The calcium salt of the higher fatty acid of 2-15 % by weight; The calcium salt of the aromatic acid of 2-10 % by weight; The polyurea compound of 1-20 % by weight; The base oil of 20-70 % by weight; Optionally also comprise the small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid.
3. lubricating grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium sulphonate-calcium naphthenate is transformed by newton's body calcium sulphonate and newton's body calcium naphthenate and obtains, and the total basicnumber of described non-newtonian fluid calcium sulphonate-calcium naphthenate is 250-450mgKOH/g.
4. lubricating grease according to claim 1 and 2, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-20.
5. lubricating grease according to claim 4, wherein, described higher fatty acid is selected from least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 and 2, wherein, described aromatic acid is that replace or unsubstituted aromatic acid, and substituting group is at least one in the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and the molecular weight of described aromatic acid is less than or equal to 550.
7. according to lubricating grease according to claim 6, wherein, described aromatic acid is selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.
8. lubricating grease according to claim 1 and 2, wherein, described polyurea compound is at least one in two polyurea compounds, four polyurea compounds, six polyurea compounds and eight polyurea compounds.
9. lubricating grease according to claim 8, wherein, described polyurea compound is two polyurea compounds, and this compound has following structure:
Wherein, R 1, R 1 'alkyl, cycloalkyl or aryl, R 3arylidene, alkylidene group or cycloalkylidene.
10. lubricating grease according to claim 9, wherein, R 1, R 1 'be the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24; R 3the arylidene of 6-30, alkylidene group or cycloalkylidene.
11. lubricating grease according to claim 10, wherein, R 1, R 1 'be the alkyl of phenyl or C1-C3 or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18, R 3be in at least one.
12. lubricating grease according to claim 1 and 2, wherein, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.
13. lubricating grease according to claim 12, wherein, described small molecules mineral acid is selected from least one in boric acid, phosphoric acid, sulfuric acid, and described lower fatty acid is selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
The preparation method of the complex calcium sulfonate in 14. claim 1-13 described in any one-Calcium naphthenate base polyurea grease, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium sulphonate-calcium naphthenate, higher fatty acid, aromatic acid, polyurea compound, oily and optionally small molecules mineral acid and/or lower fatty acid the calcium salt of part basis are mixed, 180-230 DEG C of constant temperature refining, add surplus base oil, add necessary additive, obtain finished product.
The preparation method of 15. 1 kinds of complex calcium sulfonate-Calcium naphthenate base polyurea greases, it is characterized in that, the method comprises:
(1) by newton's body calcium sulphonate, newton's body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and optionally small molecules mineral acid and/or lower fatty acid react, heat up after reaction dehydration;
(3) in step (2) gained mixture, add base oil and monoamine, or also add diamines, add vulcabond and react;
(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, adds base oil, add necessary additive, obtain finished product.
16. preparation methods according to claim 15, wherein, in step (1), by newton's body calcium sulphonate, newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, at 80-100 DEG C of constant temperature 60-90 minute.
17. preparation methods according to claim 15, wherein, in step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add aromatic acid and optionally small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 100-120 DEG C of dehydration.
18. preparation methods according to claim 15, wherein, in step (3), in step (2) gained mixture, add base oil and monoamine, stir 2-8 minute, then add vulcabond, stir 2-8 minute, the mol ratio of vulcabond and monoamine is 1:2.
19. preparation methods according to claim 15, wherein, in step (4), first at 100-120 DEG C of constant temperature 10-20 minute, are finally warmed up to 180-230 DEG C of constant temperature 5-20 minute; Add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
20. preparation methods according to claim 15, wherein, described newton's body calcium sulphonate is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, and the total basicnumber of described newton's body calcium sulphonate is 250-450mgKOH/g; Described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total basicnumber of described newton's body calcium naphthenate is 250-450mgKOH/g.
21. preparation methods according to claim 15, wherein, described transforming agent is selected from least one in fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, ether, calcium carbonate, boric acid, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, naphthenic acid, C8-C20 alkyl benzene sulphonate (ABS) and water, and the add-on of transforming agent is the 2-30% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
22. preparation methods according to claim 21, wherein, described transforming agent is selected from least one in Witco 1298 Soft Acid, naphthenic acid, methyl alcohol, Virahol, butanols, boric acid, acetic acid and water, and the add-on of transforming agent is the 6-22% of newton's body calcium sulphonate and newton's body calcium naphthenate gross weight.
23. preparation methods according to claim 15, wherein, the structural formula of described monoamine is R 1-NH 2, R 1 '-NH 2, wherein, R 1, R 1 'be the phenyl of phenyl or C1-C3 alkyl or halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10-18.
24. preparation methods according to claim 23, wherein, described monoamine is the arylamine being selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
25. preparation methods according to claim 15, wherein, the structural formula of described diamines is NH 2-R 2-NH 2, wherein, R 2the alkylidene group of to be carbon number be 2-8, or phenylene or biphenylene.
26. preparation methods according to claim 25, wherein, described diamines is selected from Ursol D, O-Phenylene Diamine, 4, the aromatic amine of 4 '-benzidine and/or be selected from the straight-chain fatty amine of quadrol, propylene diamine, 1,6-hexanediamine.
27. preparation methods according to claim 15, wherein, the structure of described vulcabond is OCN-R 3-NCO, R 3the arylidene of to be carbon number be 6-30, alkylidene group or cycloalkylidene.
28. preparation methods according to claim 27, wherein, described vulcabond is selected from least one in tolylene diisocyanate, methyldiphenyl diisocyanate, hexamethylene vulcabond, dicyclohexylmethyl vulcabond and an xylylene diisocyanate.
29. complex calcium sulfonate-Calcium naphthenate base the polyurea greases obtained by the method in claim 15-28 described in any one.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN102911761A (en) * 2012-10-24 2013-02-06 中国石油化工股份有限公司 High-temperature-resistant extreme pressure type lubricating grease composition and preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN102911761A (en) * 2012-10-24 2013-02-06 中国石油化工股份有限公司 High-temperature-resistant extreme pressure type lubricating grease composition and preparation method

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